Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 19, Issue 41, Pages 13881-13892Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201301715
Keywords
alkaloids; aza-Michael reaction; density functional calculations; nitrogen heterocycles; stereoselective synthesis
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Funding
- Spanish Ministry of Economy and Competitiveness (MINECO) [CTQ2010-14846/BQU, CTQ2010-17436, CTQ2011-29054-C02-02]
- Direccio General de Recerca (DGR, Catalunya) [2009SGR-00462]
- Gobierno de Aragon-FSE [E40]
- ICIQ Foundation
- CaixaBank
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A diastereoselective synthesis of cis-5-oxodecahydroquinolines is described in which three stereocenters are generated in a one-pot reaction. The reaction involves a lithium hydroxide-promoted Robinson annulation/intramolecular aza-Michael domino process from an achiral acyclic tosylamine-tethered -keto ester. The development and scope of this reaction was facilitated through the use of DFT-based mechanistic studies, which enabled the observed diastereodivergent course of the azacyclization to be rationalized. The varying stereochemistry and stability of the resulting decahydroquinolines was found to depend on whether a -keto ester or ketone were embedded in the substrates undergoing aminocyclization. This synthetic approach gave access not only to both diastereomeric cis-decahydroquinolines from the same precursor, but also to the corresponding trans isomers, through an epimerization processes of the corresponding N-unsubstituted cis-5-oxodecahydroquinolines. The described methodology provides advanced building-blocks with the three relative stereochemistries required for the total synthesis of phlegmarine alkaloids.
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